EP0832143A1 - Low formaldehyde emitting cross-linking agents - Google Patents
Low formaldehyde emitting cross-linking agentsInfo
- Publication number
- EP0832143A1 EP0832143A1 EP96917220A EP96917220A EP0832143A1 EP 0832143 A1 EP0832143 A1 EP 0832143A1 EP 96917220 A EP96917220 A EP 96917220A EP 96917220 A EP96917220 A EP 96917220A EP 0832143 A1 EP0832143 A1 EP 0832143A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- melamine
- range
- molar ratio
- partially alkoxymethylated
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 235
- 239000003431 cross linking reagent Substances 0.000 title description 7
- 239000004971 Cross linker Substances 0.000 claims abstract description 102
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 150000007974 melamines Chemical class 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000006266 etherification reaction Methods 0.000 claims description 14
- -1 methylol groups Chemical class 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 88
- 229920005989 resin Polymers 0.000 description 48
- 239000011347 resin Substances 0.000 description 48
- 229920003270 Cymel® Polymers 0.000 description 47
- 239000002904 solvent Substances 0.000 description 14
- 125000001841 imino group Chemical group [H]N=* 0.000 description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 12
- 238000006384 oligomerization reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 7
- 229920005692 JONCRYL® Polymers 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000003518 caustics Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 238000007069 methylation reaction Methods 0.000 description 5
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 4
- 230000011987 methylation Effects 0.000 description 4
- 229920000728 polyester Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 108091092920 SmY RNA Proteins 0.000 description 2
- 241001237710 Smyrna Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000006115 industrial coating Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BZYMNYMQGORRDS-UHFFFAOYSA-L (acetyloxy-methyl-trimethylstannyloxystannyl) acetate Chemical compound CC(=O)O[Sn](C)(OC(C)=O)O[Sn](C)(C)C BZYMNYMQGORRDS-UHFFFAOYSA-L 0.000 description 1
- MPLCFZCJLPTNPZ-UHFFFAOYSA-L (acetyloxy-propyl-tripropylstannyloxystannyl) acetate Chemical compound CCC[Sn](CCC)(CCC)O[Sn](CCC)(OC(C)=O)OC(C)=O MPLCFZCJLPTNPZ-UHFFFAOYSA-L 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NXKOSHBFVWYVIH-UHFFFAOYSA-N 2-n-(butoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical class CCCCOCNC1=NC(N)=NC(N)=N1 NXKOSHBFVWYVIH-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical class COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000011993 High Performance Size Exclusion Chromatography Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JLHADLTXDDGZFX-UHFFFAOYSA-L [[acetyloxy(dibutyl)stannyl]oxy-dibutylstannyl] acetate Chemical compound CCCC[Sn](CCCC)(OC(C)=O)O[Sn](CCCC)(CCCC)OC(C)=O JLHADLTXDDGZFX-UHFFFAOYSA-L 0.000 description 1
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- IZDFRICNRCPQQZ-UHFFFAOYSA-N benzhydryl dihydrogen phosphate Chemical class C=1C=CC=CC=1C(OP(O)(=O)O)C1=CC=CC=C1 IZDFRICNRCPQQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- HZXXNQUMSGYIKQ-JRYLAINFSA-N bis(6-methylheptyl) (Z)-but-2-enedioate dibutyltin Chemical compound CCCC[Sn]CCCC.CC(C)CCCCCOC(=O)\C=C/C(=O)OCCCCCC(C)C HZXXNQUMSGYIKQ-JRYLAINFSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- SVSRQMUJHHQAAX-UHFFFAOYSA-N dibenzyltin Chemical compound C=1C=CC=CC=1C[Sn]CC1=CC=CC=C1 SVSRQMUJHHQAAX-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- OVQABVAKPIYHIG-UHFFFAOYSA-N n-(benzenesulfonyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NS(=O)(=O)C1=CC=CC=C1 OVQABVAKPIYHIG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
Definitions
- This invention relates to low free formaldehyde and low N-methylol group containing melamine derived crosslinker compositions and to low formaldehyde emitting thermosetting coating compositions based on these crosslinkers compositions, which coating compositions can provide durable, substantially defect-free films upon curing.
- the low formaldehyde emitting thermosetting coating compositions in accordance with the present invention contain, in their broadest concept, a low free formaldehyde and low N-methylol group containing partially alkoxymethylated high NH (high imino) melamine crosslinking agent and a polyfunctional material containing functional groups capable of reacting therewith.
- a problem with melamine formaldehyde resins is that they emit formaldehyde during the curing process, creating potential health and safety hazards and environmental pollution problems. Because of the health, safety and environmental concerns associated with large scale use of compositions containing melamine-formaldehyde crosslinking agents, demand for lower formaldehyde emitting coatings has steadily increased in recent years providing an incentive to find a practical solution to the problem.
- the present invention is a liquid, partially alkoxymethylated melamine crosslinker composition having from about 2.6 to about 4.6 moles of combined formaldehyde per mole of melamine, from about 1.4 to about 4.4 moles of alkyl per mole of melamine, from about 1.3 to about 3.4 moles of NH per mole of melamine, a free formaldehyde level of less than about 0.5 weight percent, and preferably less than about 0.3 weight percent, based on 100 percent solids, and an N-methylol level of less than about 6.0 weight percent, preferably less than about 5.0 weight percent, and more preferably less than about 4.0 weight percent, based on 100 percent solids.
- the present invention is further a low formaldehyde emitting curable composition which, when cured, produces a formaldehyde emission of less than about 7.5 weight percent based on the weight of the crosslinker, comprising the above-described crosslinker of the present invention and a polyfunctional material reactive therewith. These compositions are rapid curing but do not emit unacceptably high levels of formaldehyde.
- the present invention is still further a process for preparing the crosslinkers of the invention said process comprising the step of contacting a liquid partially alkoxymethylated melamine crosslinker and a reagent selected from the group consisting of an amino group containing compound and an etherification agent, as described in further detail below.
- the present invention is still further a method of coating a substrate by applying onto a substrate the low formaldehyde emitting curable compositions of the invention and then ⁇ heat curing the so applied coating.
- the present invention is crosslinked film or coated article prepared by the above method of coating.
- Such crosslinked films possess good hardness, impact resistance and solvent resistance, and are substantially surface defect-free with desirable appearance characteristics such as gloss and lack of pinholes or blisters.
- the Melamine Crosslinking Agent has from about 2.6 to about 4.6 moles of combined formaldehyde per mole of melamine, from about 1.4 to about 4.4 moles of alkyl per mole of melamine, from about 1.3 to about 3.4 moles of NH per mole of melamine, a free formaldehyde level of less than about 0.5 weight percent, preferably less than about 0.3 weight percent, based on 100 percent solids, and an N-methylol level of less than about 6.0 weight percent, preferably less than about 5.0 weight percent, and more preferably less than about 4.0 weight percent, based on 100 percent solids.
- the combined formaldehyde to melamine molar ratio is preferably in the range of from about 2.6 to about 3.4, and more preferably in the range of from about 3.0 to about 3.4; the alkyl to melamine molar ratio is preferably in the range of from about 1.4 to about 3.2, and more preferably in the range of from about 2.4 to about 2.8; and the NH to melamine molar ratio is preferably in the range of from about 1.8 to about 3.4, and more preferably in the range of from about 2.0 to about 2.8.
- the combined formaldehyde to melamine molar ratio is preferably in the range of from about 3.6 to about 4.6, and more preferably is in the range of from about 3.8 to about 4.2; the alkyl to melamine molar ratio is preferably in the range of from about 2.4 to about 4.4, and more preferably in the range of from about 2.6 to about 3.8; and the NH to melamine molar ratio is preferably in the range of from about 1.3 to about 2.4, and more preferably in the range of from about 1.4 to about 1.8.
- moderately high NH crosslinker may be mentioned one wherein the combined formaldehyde- to melamine molar ratio in the range of from about 3.8 to about 4.0, the alkyl to melamine molar ratio in the range of from about 2.6 to about 3.0, and an NH to melamine molar ratio in the range of from about 1.4 to about 1.6.
- the liquid partially alkoxymethylated melamine crosslinker compositions of the invention When cured, the liquid partially alkoxymethylated melamine crosslinker compositions of the invention produce a formaldehyde emission of less than about 7.5 weight percent based on the weight of the crosslinker, and in some cases, particularly in cases such as those prepared by a process which includes both treatment with an amino group containing compound and etherification steps as described below, they produce a formaldehyde emission of less than about 4.3 weight percent based on the weight of the crosslinker.
- the liquid partially alkoxymethylated melamine crosslinkers of the present invention preferably comprise at least 30 weight percent monomeric species, the balance being a complex mixture of products including, for example, monomeric bis-, tris-, and tetra- substituted alkoxymethylated melamine derivatives, N,N'-bis-alkoxyalkyl melamines, N,N',N"- tris-alkoxyalkyl melamines, and N,N',N",N"-tetrakis-alkoxyalkyl melamines, oligomers derived from the di-, tri-, and tetra-substituted derivatives, and other variations recognizable by those of ordinary skill in the relevant art.
- the preferred crosslinker for use in the present invention preferably comprises from about 40 wt% to about 65 wt% monomer.
- Wt% monomer for the purposes of the present invention is equated with the area percent of the monomeric portion of a curve determined by analysis of the partially alkoxymethylated melamine crosslinker by well-known high performance size exclusion chromatography techniques.
- Each alkoxy group of the present partially alkoxymethylated melamines is independently based on an alkyl group preferably selected from the group consisting of linear, branched and cyclic alkyls of 1 to 20 carbon atoms.
- Especially preferred alkyl groups are lower alkyls of 1 to 8 carbon atoms including, for example, methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, iso-butyl, tert-butyl, 1-pentyl, 1-hexyl, cyclohexyl and 2-ethyl-1-hexyl.
- the most preferred alkyls are methyl, ethyl and butyl groups.
- crosslinkers having mixed alkyl groups such as mixed methyl and butyl groups.
- the low formaldehyde emitting curable compositions of the invention are characterized as being a low formaldehyde emitting compositions which, when cured, produce a formaldehyde emission of less than about 7.5 weight percent, preferably less than about 6.5 weight percent, and more preferably less than about 4.3 weight percent,- based on the weight of the crosslinker.
- the curable compositions of the present invention can be based on any well-known melamine resin crosslinked composition in which all or a portion of the existing melamine resin is replaced with the crosslinker composition of the present invention.
- these curable composition may be characterized as comprising (i) the crosslinker compositions of the present invention and (ii) a polyfunctional material capable of reacting therewith.
- the polyfunctional material containing a functionality capable of reacting with the liquid partially alkoxymethylated melamine crosslinkers of the invention under normal coatings cure conditions are well known backbone resins widely used in amino resin crosslinked coatings.
- These resins contain at least two reactive functionalities each preferably independently selected from the group consisting of hydroxy, carboxy, amino, amido, carbamato, mercapto, and a group convertible thereto.
- the preferred polyfunctional materials are hydroxyfunctional or carboxyfunctional acrylic or polyester backbone resins, with hydroxyfunctional materials being especially preferred.
- Illustrative examples of polyfunctional materials include acrylic resins which may be obtained by the copolymerization of acrylic or methacrylic esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or methacrylate, optionally with simultaneous use of additional vinyl compounds such as, for example, styrene.
- polyfunctional materials also include polyester resins which may be obtained, for example, by the reaction of polycarboxylic acids with excess quantities of polyhydric alcohols.
- Suitable hydroxyfunctional resins also include epoxy or polyurethane prepolymers, alkyds, and the like.
- such resins may have pendent or terminal hydroxyl functionalities and preferably have the following characteristics: weight average molecular weights (Mw) of from about 750 to about 7000, and more preferably from about 2000 to about 5000; and hydroxyl numbers of from about 20 to about 100 mg KOH/g resin, more preferably from about 25 to about 60 mg KOH/g resin, and especially from about 25 to about 40 mg KOH/g resin.
- Mw weight average molecular weights
- hydroxyl numbers of from about 20 to about 100 mg KOH/g resin, more preferably from about 25 to about 60 mg KOH/g resin, and especially from about 25 to about 40 mg KOH/g resin.
- materials having much higher molecular weights are generally preferred.
- Other suitable hydroxyl functional resins will be readily recognized by those of ordinary skill in the art.
- suitable polyfunctional hydroxy group containing materials include JONCRYL ® 500 acrylic resin (S.C.Johnson & Sons, Racine, WI), ACRYLOID ® AT-400 acrylic resin (Rohm & Haas, Philadelphia, PA), CYPLEX ® 1531 polyester resin (Cytec Industries, West Paterson, NJ), CARGILL ® 3000 and 5776 polyester- resins (Cargill, Minneapolis, MN), TONE ® polyester resin (Union Carbide, Danbury, CT), K-FLEX ® XM-2302 and XM-2306 resins (King Industries, Norwalk, CT), CHEMPOL ® 11- 1369 resin (Cook Composites and Polymers, Port Washington, WI), JONCRYL ® 540 acrylic emulsion polymer (S.C.Johnson & Sons, Racine, WI), RHOPLEX ® AC-1024 acrylic emulsion resin (Rohm & Haas, Philadelphia, PA), XC
- carboxyfunctional resins examples include CRYLCOAT ® solid carboxy terminated polyester resin (UCB CHEMICALS USA, Smyrna, GA), RUCOTE ® 101 polyester resin (Ruco Polymer Corporation, Hicksville, N.Y.), ALFTALAT ® AN 745 hydroxyfunctional polyester resin (Hoechst Corporation) and ARAKOTE ® 3010 carboxy terminated polyester (Ciba-Geigy Corporation, Ardsley, N.Y.).
- liquid polyfunctional hydroxy group containing materials are preferred; however, a solid polyfunctional hydroxy group containing material may be used in cases when the solids are soluble in the solvent used in a particular formulation.
- Resins containing amino, amido, carbamato, or mercapto groups, including groups convertible thereto, may be prepared by known methods including copolymerizing a suitably functionalized monomer with a comonomer capable of copolymerizing therewith.
- the curable composition of the present invention may further comprise a cure catalyst, examples of which again are in general well known to those of ordinary skill in the art.
- the cure catalysts usable in the present invention include, for example, sulfonic acids, aryl, alkyl, and aralkyl acid phosphates, aryl, alkyl, and aralkyl acid pyrophosphates, carboxylic acids, sulfonimides, mineral acids, Lewis acids, organometallic compounds and a mixture thereof. Of the above acids, sulfonic acids are preferred.
- sulfonic acids examples include benzenesulfonic acid, para-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and a mixture thereof.
- Examples of the aryl, alkyl, and aralkyl phosphates and pyrophosphates include phenyl, para-tolyl, methyl, ethyl, benzyl, diphenyl, di-para-tolyl, di ⁇ methyl, di-ethyl, di-benzyl, phenyl-para-tolyl, methyl-ethyl, phenyl-benzyl phosphates and pyrophosphates.
- Examples of the carboxylic acids include benzoic acid, formic acid, acetic acid, propionic acid, butyric acid, dicarboxylic acids such as oxalic acid, fluorinated acids such as trifluoroacetic acid, and the like.
- Examples of the sulfonimides include dibenzene sulfonimide, di-para-toluene sulfonimide, methyl-para-toluene sulfonimide, dimethyl sulfonimide, and the like.
- Examples of the mineral acids include nitric acid, sulfuric acid, - phosphoric acid, poly-phosphoric acid, and the like.
- Examples of the Lewis acids include boron and aluminum halides.
- organometallic compounds examples include organotin compounds such as dibutyltin di-2-ethylhexoate, dibutyltin diisooctyl maleate, dibenzyltin di- 2-ethylhexoate, dibutyltin diiaurate, dimethyltin dilaurate, tetrabutyl diacetoxy distannoxane, tetramethyl diacetoxy distannoxane, tetrapropyl diacetoxy distannoxane, dibutyltin dichloride, and the like.
- organotin compounds such as dibutyltin di-2-ethylhexoate, dibutyltin diisooctyl maleate, dibenzyltin di- 2-ethylhexoate, dibutyltin diiaurate, dimethyltin dilaurate, tetrabutyl diacetoxy distannoxane, te
- the curable composition of the present invention may also contain, as an optional ingredient, a medium such as a liquid medium to aid the uniform application and transport of the curable composition. Any or all of the ingredients of the curable composition may be contacted with the liquid medium. Moreover, the liquid medium may permit formation of a dispersion, emulsion, invert emulsion, or solution of the ingredients of the curable composition. Particularly preferred is a liquid medium which is a solvent for the curable composition ingredients. Suitable such solvents include aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, amides, alcohols, water, compounds having a plurality of functional groups such as those having an ether and an ester group, and a mixture thereof.
- a medium such as a liquid medium to aid the uniform application and transport of the curable composition. Any or all of the ingredients of the curable composition may be contacted with the liquid medium.
- the liquid medium may permit formation of a dispersion, emul
- the low formaldehyde emitting curable compositions of the invention may also include varying amounts of other conventional additives well known to those of ordinary skilled in the art of coating, as exemplified by the previously incorporated references. Included among these are additives such as fillers, antioxidants, ultraviolet light stabilizers, pigments such as, for example, Ti0 2 pigment, flow control agents, plasticizers, mold release agents, corrosion inhibitors, and the like.
- additives such as fillers, antioxidants, ultraviolet light stabilizers, pigments such as, for example, Ti0 2 pigment, flow control agents, plasticizers, mold release agents, corrosion inhibitors, and the like.
- the relative amounts of the components in accordance with the present invention are not in general critical. Any proportion of ingredients may be employed that results in a curable coating composition capable of providing a durable, substantially surface defect- free finish after curing.
- the ratio of the polyfunctional material to the crpsslinking agent is in the range of from about 99:1 to about 0.5:1.
- the weight percent of the cure catalyst, if present, is generally in the range of from about 0.01 to about 3.0 wt% based upon the combined weight of the backbone resin and crosslinker.
- the amount of crosslinker employed is typically in the range of from about
- the binder which, for the purposes of the present invention, is the combined weight of the crosslinker and the polyfunctional material (backbone resin).
- the preferred amount of the polyfunctional material employed is typically in the range of from about 70 to about 97 wt%, and more preferably in the range of from about 80 to about 85 wt%, of- the binder.
- the process for preparing the crosslinkers of the present invention comprises the step of contacting a liquid partially alkoxymethylated melamine resin and a reagent selected from the group consisting of an amino group containing compound and an etherification agent.
- the contacting is carried out at a temperature and length of time sufficient to produce the crosslinkers of the invention which contain less than about 0.5 weight percent free formaldehyde and less than about 6.0 weight percent N-methylol groups, both numbers being based on 100 percent solids.
- the N-methylol group level is less than about 5.0 weight percent and, more preferably, less than about 4.0 weight percent.
- the starting material is a liquid partially alkoxymethylated melamine derivative having 2.6 to 4.6 moles of combined formaldehyde per mole of melamine, 1.4 to 4.4 moles of alkyl per mole of melamine, 1.3 to 3.4 moles of NH per mole of melamine and relatively high N-methylol levels (e.g., greater than 6.0 wt% based on 100 percent solids) and/or free formaldehyde levels (e.g., greater than 0.5 wt% based on 100 percent solids), and includes resins such as CYMEL ® 322 crosslinker, CYMEL ® 323 crosslinker, CYMEL ® 324 crosslinker, CYMEL ® 325 crosslinker, CYMEL ® 327 crosslinker, CYMEL ® 350 crosslinker, CYMEL ® 370 crosslinker, CYMEL ® 373 crosslinker, CYMEL ® 380 crosslinker,
- CYMEL ® 322 high methylol/imino content, moderate degree of oligomerization (1.75)
- CYMEL ® 323 high methylol/imino content, moderate degree of oligomerization (1.8)
- CYMEL ® 325 high methylol/imino content, higher degree of oligomerization
- CYMEL ® 350 high methylol/imino content, moderate degree of oligomerization (1.55)
- CYMEL ® 370 high methylol/imino content, higher degree of oligomerization
- CYMEL ® 324 methoxy/n-butoxy, high methylol/imino content, higher degree of oligomerization (2.3)
- Other suitable liquid partially alkoxymethylated melamine derivatives which are not commercially available may be easily prepared from melamine, formaldehyde, and an alcohol at the desired proportions using well known procedures such as those described in, for example, previously incorporated US4101520, US4433143 and US4425466, and well known modifications thereof.
- melamine may be used as a starting material to produce a partially alkoxymethylated derivative by reaction with an etherification agent, which can be further reacted (for example, in multiple steps) with the etherification agent and/or amino group containing compound.
- One preferred process is, indeed, a triple etherification of melamine as demonstrated in an example below.
- the starting material (containing relatively high levels of N-methylol groups and varying levels of free formaldehyde) and a reagent selected from the group consisting of an amino group containing compound and an etherification agent are preferably contacted at a temperature in the range of from about 25°C to about 120°C, and for a period in the range of about 10 minutes to about 10 hours, to produce a liquid partially alkoxymethylated melamine crosslinker containing less than about 0.5 weight percent free formaldehyde based on 100 percent solids and less than about 6.0 weight percent N-substituted methylol groups based on 100 percent solids. If desired, the procedure may be repeated to further reduce the free formaldehyde and the N-substituted methylol group levels.
- the amino group containing compound referred to above is preferably selected from the group consisting of amines, aminotriazines, amides, sulfonamides, phosphoramides, ureas, carbamates, ammonia and a mixture thereof.
- Amines which are effective in reducing the free formaldehyde and the N-substituted methylol group levels include ammonia and • compounds which contain primary and or secondary amine groups. A mixture containing a plurality of amines may also be used.
- the amino group containing compound may monofunctional or it may be polyfunctional and it may be monomeric or polymeric. Polyfunctional or polymeric amino group containing compounds which are relatively insoluble in the resin are preferred.
- the etherification agent preferably comprises an alcohol and an acid catalyst.
- Alcohols corresponding to the alkyls referred to above, the preferred being alcohols of 1 to 8 carbon atoms, and especially methanol.
- acids are usable in the etherification reaction, including the acid catalysts mentioned above, and preferably the strong mineral acids.
- the process may further require filtering insoluble materials formed during the reaction and/or it may require stripping volatiles including any unreacted volatile alcohol such as methanol.
- the method of coating of the present invention produces a formaldehyde emission of less than about 7.5 weight percent based on the weight of the crosslinker.
- the method generally comprises: (a) applying onto a substrate a curable composition as described above; and thereafter (b) heat-curing the so-applied curable composition.
- curable compositions containing a liquid medium such as a solvent may be advantageously used. Contacting may be carried out by dipping, spraying, padding, brushing, flowcoating, electrocoating or electrostatic spraying. Typically, the solvent is allowed to partially evaporate to produce a uniform coating on the substrate. Thereafter, the compositions may be fully cured by further application of heat at a temperature in the range of from about 25 °C to about 300 °C and preferably at a temperature in the range of from about 80 °C to about 220 °C for a period- of time preferably in the in the range of about 5 minutes to about 30 minutes to obtain a fully cured coating, film, or object prepared in accordance with the method of the invention.
- a liquid medium such as a solvent
- the heat cured compositions of this invention may be employed as coatings in the general areas of coatings such as original equipment manufacturing (OEM) including automotive coatings, general industrial coatings including industrial maintenance coatings, architectural coatings, coil coatings, can coatings, wood coatings, and low temperature cure automotive refinish coatings. They are usable as coatings for wire, appliances, automotive parts, furniture, pipes, machinery, and the like. Suitable surfaces include metals such as steel and aluminum, plastics, wood, and glass.
- the low formaldehyde emitting compositions of the present invention are also well suited for use to refinish automotive parts and to coat heat sensitive substrates such as wood.
- crosslinkers of the present invention may also be used as binders for non ⁇ wovens, as textile treatment agents for permanent press textiles, as coating insolublizers for gellation of starch in paper, and as colloidal wet and dry strength agents in paper manufacture.
- curable compositions containing them may be used in adhesives, decorative laminated boards and crosslinked molded articles.
- CYMEL ® 327 resin 100 g
- a 30 wt % solution of aqueous ammonia 17 g
- the solution was kept under these conditions for 6 hrs., the volatiles were removed under reduced pressure while maintaining the pH between 10.0 to 10.5 then, after addition of isobutanol, the insolubles were filtered.
- the properties of the modified resin are listed in Table 2.
- Sybron Chemicals, Inc. Birmingham, N.J., and may be prepared by the reaction of an epoxide and a polyamine). The mixture was cooled to ambient temperature, the beads were filtered, the methanol was evaporated and isobutanol was added. The properties of the modified resin are listed in Table 3.
- XR-374 is a product of Sybron Chemicals, Birmingham, N.J., and may be prepared from divinylbenzene and N,N'-dimethyl-3-aminopropyl acrylamide).
- the mixture was cooled to ambient temperature, the beads were filtered, the methanol was evaporated and isobutanol was added.
- Table 3 The properties of the modified resin are listed in Table 3.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
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Abstract
Description
Claims
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US48898795A | 1995-06-08 | 1995-06-08 | |
US488987 | 1995-06-08 | ||
PCT/US1996/009054 WO1996041826A1 (en) | 1995-06-08 | 1996-06-05 | Low formaldehyde emitting cross-linking agents |
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EP0832143A1 true EP0832143A1 (en) | 1998-04-01 |
EP0832143B1 EP0832143B1 (en) | 1999-01-27 |
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US (1) | US5821323A (en) |
EP (1) | EP0832143B1 (en) |
JP (1) | JPH11508290A (en) |
KR (1) | KR100426264B1 (en) |
AT (1) | ATE176253T1 (en) |
CA (1) | CA2222988C (en) |
DE (1) | DE69601468T2 (en) |
DK (1) | DK0832143T3 (en) |
ES (1) | ES2127641T3 (en) |
GR (1) | GR3029630T3 (en) |
WO (1) | WO1996041826A1 (en) |
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US20030022184A1 (en) * | 1996-02-12 | 2003-01-30 | Oncormed. Inc. | Coding sequences of the human BRCA1 gene |
KR19990087318A (en) * | 1996-03-01 | 1999-12-27 | 마이클 제이. 켈리 | Cyclic imido-1,3,5-triazine crosslinker |
US6045872A (en) * | 1998-05-01 | 2000-04-04 | Basf Corporation | Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein |
US5972422A (en) * | 1998-05-01 | 1999-10-26 | Basf Corporation | Method for low bake repair of composite color-plus-clear coatings, and compositions for use therein |
US7381347B2 (en) * | 2003-03-31 | 2008-06-03 | Cytec Technology Corp. | Crosslinking composition |
CN104562689A (en) * | 2013-10-16 | 2015-04-29 | 圣戈班磨料磨具有限公司 | Backing material treated by amino resin, coated abrasive tool product containing and utilizing backing material as well as preparation method of backing material |
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JPS51125102A (en) * | 1974-09-18 | 1976-11-01 | Sumitomo Chem Co Ltd | A resinous composition for use in coating compound |
DE2516349C3 (en) * | 1975-04-15 | 1981-03-19 | Cassella Ag, 6000 Frankfurt | Process for the preparation of etherified methylol melamines and benzoguanamines |
US4183832A (en) * | 1975-04-30 | 1980-01-15 | Saint-Gobain Industries | Aqueous solutions of etherified melamine-formaldehyde resins with long shelf life and low free formaldehyde content |
US4169825A (en) * | 1975-05-15 | 1979-10-02 | The Sherwin-Williams Company | High solids coating compositions |
US4101520A (en) * | 1976-07-19 | 1978-07-18 | American Cyanamid Company | Methylated, methylolated melamine composition |
US4129681A (en) * | 1976-10-20 | 1978-12-12 | Monsanto Company | Coating compositions comprising alkoxymethylaminotriazines, polyols and polyhydroxy oligomers |
US4276212A (en) * | 1978-12-11 | 1981-06-30 | E. I. Du Pont De Nemours And Company | High solids coating composition of a low molecular weight acrylic polymer and an alkylated melamine cross-linking agent |
US4330458A (en) * | 1980-04-28 | 1982-05-18 | E. I. Du Pont De Nemours And Company | High solids coating composition of a blend of a low molecular weight acrylic polymer and a medium molecular weight acrylic polymer and an alkylated melamine cross-linking agent |
US4433143A (en) * | 1981-09-09 | 1984-02-21 | Monsanto Company | Methylated methylolated melamine composition |
US4425466A (en) * | 1981-09-09 | 1984-01-10 | Monsanto Company | Coating compositions comprising a methylated methylolated melamine |
US4374164A (en) * | 1981-12-14 | 1983-02-15 | American Cyanamid Company | High solids polymer resin coating composition containing amino resin cross-linking agent |
US4873298A (en) * | 1986-12-16 | 1989-10-10 | E. I. Du Pont De Nemours And Company | Polysiloxane graft copolymers, flexible coating compositions comprising same and branched polysiloxane macromers for preparing same II |
DE3905913A1 (en) * | 1989-02-25 | 1990-09-13 | Basf Ag | AMINO SOLVENT SOLUTIONS WITH LOW ELECTRICAL CAPACITY |
US5155201A (en) * | 1989-07-13 | 1992-10-13 | Akzo N.V. | Polyurethane polyols and high solids coatings therefrom |
DD301293A7 (en) * | 1989-08-08 | 1992-11-19 | Wittenberg Stickstoff Ag | METHOD FOR THE PRODUCTION OF BUTOXYLATED AMINO-CARCE PARTICLE SENSITIVES |
JPH04130168A (en) * | 1990-09-20 | 1992-05-01 | Nippon Paint Co Ltd | Clear coating material and method for forming coating film |
-
1996
- 1996-06-05 AT AT96917220T patent/ATE176253T1/en not_active IP Right Cessation
- 1996-06-05 CA CA002222988A patent/CA2222988C/en not_active Expired - Fee Related
- 1996-06-05 EP EP96917220A patent/EP0832143B1/en not_active Revoked
- 1996-06-05 DE DE69601468T patent/DE69601468T2/en not_active Expired - Fee Related
- 1996-06-05 WO PCT/US1996/009054 patent/WO1996041826A1/en active IP Right Grant
- 1996-06-05 KR KR1019970708535A patent/KR100426264B1/en not_active IP Right Cessation
- 1996-06-05 JP JP9503151A patent/JPH11508290A/en active Pending
- 1996-06-05 ES ES96917220T patent/ES2127641T3/en not_active Expired - Lifetime
- 1996-06-05 DK DK96917220T patent/DK0832143T3/en active
-
1997
- 1997-08-15 US US08/920,202 patent/US5821323A/en not_active Expired - Fee Related
-
1999
- 1999-03-09 GR GR990400720T patent/GR3029630T3/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9641826A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP0832143B1 (en) | 1999-01-27 |
KR100426264B1 (en) | 2004-06-30 |
JPH11508290A (en) | 1999-07-21 |
DE69601468T2 (en) | 1999-08-05 |
CA2222988C (en) | 2003-01-14 |
DE69601468D1 (en) | 1999-03-11 |
CA2222988A1 (en) | 1996-12-27 |
KR19990022056A (en) | 1999-03-25 |
US5821323A (en) | 1998-10-13 |
GR3029630T3 (en) | 1999-06-30 |
ES2127641T3 (en) | 1999-04-16 |
WO1996041826A1 (en) | 1996-12-27 |
ATE176253T1 (en) | 1999-02-15 |
DK0832143T3 (en) | 1999-09-13 |
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